Methods for making free fatty acids from soaps using thermal hydrolysis followed by acidification

ABSTRACT

Provided are methods, processes and systems for treating a soapstock. In alternative embodiments, provided are systems and methods for treating a soapstock to generate free fatty acids and/or fatty acid derivatives, e.g. fatty acid alkyl esters. In alternative embodiments, provided are systems and methods for realizing the full fatty acid yield of a soapstock by first converting substantially all of the saponifiable material in a soapstock to salts of fatty acids (soaps) and acidulating the soaps to generate free fatty acids and/or fatty acid derivatives, e.g. fatty acid alkyl esters, wherein the soapstock comprises soaps and saponifiable lipids, e.g. glycerides and/or phospholipids, and the generating of free fatty acids and/or fatty acid is achieved.

RELATED APPLICATIONS

This U.S. National Phase patent application claims priority under 35U.S.C. § 371 to Patent Convention Treaty (PCT) International ApplicationPCT/US2017/050321, filed Sep. 6, 2017, now pending, which claims thebenefit of priority under 35 U.S.C. § 119(e) to U.S. ProvisionalApplication Ser. No. 62/385,883, now expired, filed Sep. 9, 2016. Theaforementioned applications are expressly incorporated herein byreference in their entirety and for all purposes.

TECHNICAL FIELD

The present invention generally provides processes for treating asoapstock and making free fatty acids. Provided are systems and methodsfor treating a soapstock or any composition comprising a mixture oftriglycerides of fatty acids to generate free fatty acids and/or fattyacid derivatives, e.g. fatty acid alkyl esters such as fatty acid methylesters. Provided are systems and methods for realizing the full fattyacid yield of a soapstock by first thermally hydrolyzing thesaponifiable material in a soapstock and then acidulating the soaps togenerate free fatty acids and/or fatty acid derivatives, e.g. fatty acidalkyl esters. In alternative embodiments, the soapstock comprises a soapor any saponifiable lipid, e.g. glycerides, triglycerides and/orphospholipids, and the generating of free fatty acids and/or fatty acidis achieved.

BACKGROUND

Crude (unrefined) animal and vegetable oils (referred to hereincollectively as “natural oils”) are typically subjected to a variety ofprocessing steps to remove specific undesirable components of the crudeoil prior to sale. The type, number, and sequencing of processing stepscan vary depending on the crude oil feedstock, refinery type (e.g.physical vs. alkaline) and configuration, target product markets, andthe like. In general, crude natural oils are refined to remove excessquantities of “gums” (comprised primarily of phospholipids), free fattyacids, as well as various coloring components and volatile compounds.

Once removed from the crude oil, the refining byproducts are either solddirectly into low-value markets such as animal feed, or furtherprocessed into higher-value products. Two major byproducts of thechemical refining processes of natural oils are soapstock and gums. Inmost natural oil refineries utilizing the chemical refining process,phosphoric acid or an equivalent acid is added to the crude oil toincrease the solubility of the phospholipids (gums) in water. Next, astrong base, typically sodium hydroxide (NaOH) is added, reacting withthe free fatty acids in the oil to form soaps (salts of free fattyacids). Water is then added to the oil to remove the soaps andsolubilized gums. Soapstock is typically acidulated to generate freefatty acids. Gums are typically sold into low-value animal feed marketsor upgraded to food-grade emulsifiers, e.g. lecithin.

In most chemical refining configurations, additional waste streams aregenerated which represent low- or negative-value byproducts. Forexample, it typically necessary to perform an additional water wash onthe oil after the majority of the gums and soaps have been removed. Thelipid content of this washwater (referred to as Soapstock Makeup) cancontain from about 5% to about 20% soaps and other lipids, but the lipidcontent is generally not sufficiently high to justify the costs offurther processing into value added products. In addition, all of theabove referenced byproduct streams from the chemical refining processcontain various amounts of saponifiable (triglyceride-comprising)material that are not converted to free fatty acids.

SUMMARY

In alternative embodiments, provided are processes and systems fortreating or processing a soapstock. In alternative embodiments, providedare systems and methods for treating a soapstock, or any triglyceridecomprising material, to generate free fatty acids and/or fatty acidderivatives, e.g. fatty acid alkyl esters such as fatty acid methylesters.

In alternative embodiments, provided are methods and systems forgenerating free fatty acids from a mixed lipid feedstock. In alternativeembodiments, a mixed lipid feedstock, e.g., from an animal or plantsource, is provided. The feedstock is first heated and pressurized(hereinafter referred “thermal hydrolysis”) to produce fatty acids. Thereacted first mixture is combined with an acid or acid solution, therebyacidulating soaps unreacted in the first step to generate additionalfree fatty acids.

In alternative embodiments, the method further comprises additionalsteps, e.g., as described herein. For example, in alternativeembodiments, the generated free fatty acids can be esterified with analcohol to form a second mixture, thereby esterifying substantially allof the free fatty acids to generate fatty acid alkyl esters. Thegenerated free fatty acids can be separated, isolated, or purified intoseparate fractions. The mixed lipid feedstock can be selected from thegroup consisting of a soapstock, a washwater comprising soaps, and acombination thereof as generated during the chemical refining of a crudenatural oil. The mixed lipid feedstock can be a tall oil soapstock. Thecrude natural oil can be a vegetable oil. The vegetable oil can beselected from the group consisting of soybean oil, canola oil, rapeseedoil, corn oil, rice oil, sunflower oil, peanut oil, sesame oil, palmoil, algae oil, jatropha oil, castor oil, safflower oil, grape seed oil,and any combination of vegetable oils. The mixed lipid feedstock canfurther comprise: water, soaps, phospholipids, saponifiable material,and unsaponifiable material. The acid can be carbonic acid. The carbonicacid can be generated by adding carbon dioxide to the thermal hydrolysisproduct mixture, thereby causing the carbon dioxide to react with thewater in the thermal hydrolysis product mixture to form carbonic acid.

In alternative embodiments, also provided are methods and systems forgenerating free fatty acids from a mixed lipid feedstock. In alternativeembodiments, a mixed lipid feedstock is provided and subjected tothermal hydrolysis. The mixture is allowed to react in a reactionvessel. In alternative embodiments, carbon dioxide, if used, isintroduced into the reacted mixture in the reaction vessel to form afirst carbonic acid within the reaction vessel. Alternatively, acarbonic acid can be mixed with the reacted mixture within the reactionvessel. In alternative embodiments, the carbonic acid and reactedmixture is allowed to settle within the reaction vessel. A first aqueouslayer can be drained from the reaction vessel.

In alternative embodiments, the carbon dioxide is introduced as agaseous flow of carbon dioxide into the reaction vessel. The carbondioxide can be introduced as a liquid flow of carbon dioxide into thereaction vessel. In a second acidulation reaction, carbon dioxide can beintroduced into the reacted mixture in the reaction vessel to form asecond carbonic acid within the reaction vessel. The second carbonicacid (of the second acidulation reaction) can be mixed with the reactedmixture within the reaction vessel. The second carbonic acid and reactedmixture can be allowed to settle within the reaction vessel. A secondaqueous layer (of the second acidulation reaction) can be drained fromthe reaction vessel. In an alternative embodiment, an objective is toreach an equilibrium between carbonic acid and sodium bicarbonate, andthis can be achieved through multiple acidulation steps as required bythe different feedstocks, for example, optionally up to 20 acidulationsteps, or more if desired or necessary, can be used to achieve a high,or the highest possible, yield of fatty acids.

In alternative embodiments, provided are methods for generating freefatty acids from a castor oil. In alternative embodiments, the castoroil is reacted via thermal hydrolysis in a reaction vessel. Carbondioxide is introduced into the reacted mixture in the reaction vessel toform a carbonic acid within the reaction vessel. The carbonic acid andthe reacted mixture is then mixed within the reaction vessel. Thecarbonic acid and reacted mixture is allowed to settle within thereaction vessel. An aqueous layer is drained from the reaction vessel.

In alternative embodiments, the carbon dioxide is introduced as agaseous or liquid flow of carbon dioxide into the reaction vessel. In asecond acidulation reaction, carbon dioxide can be introduced into thereacted mixture in the reaction vessel to form a second carbonic acidwithin the reaction vessel. The second carbonic acid can be mixed withthe reacted mixture within the reaction vessel. The second carbonic acidand reacted mixture can be allowed to settle within the reaction vessel.A second aqueous layer (from the second acidulation reaction) can bedrained from the reaction vessel.

In alternative embodiments, provided are methods and processes forgenerating free fatty acids from a mixed lipid feedstock using a thermalhydrolysis reaction, the method or process comprising:

(a) providing an aqueous solution or mixture comprising a mixed lipidfeedstock, and

-   -   wherein optionally the mixed lipid feedstock comprises: a        soapstock; a triglyceride comprising material; a saponifiable        material (optionally a glyceride or a phospholipid); a tall oil        (“liquid rosin” or tall oil) soapstock; a gums product        (optionally chemically or enzymatically derived); a crude        biodiesel; a fatty acid (optionally from a distillation bottom);        a fat splitter emulsion (optionally purged from fat splitter due        to accumulation when recycled); or, any combination thereof,    -   and optionally the mixed lipid feedstock comprises a soapstock,        a wash-water comprising soaps or a combination thereof,        optionally generated during the chemical refining of a crude        natural oil,    -   and optionally the mixed lipid feedstock is derived from a        biomass, a crude natural oil, or a plant or an animal source        (optionally a tallow);    -   and optionally the mixed lipid feedstock is derived from        enzymatic degumming of edible and inedible oils; and

(b) heating and pressurizing the aqueous solution or mixture comprisingthe mixed lipid feedstock in a thermal hydrolysis reaction underconditions comprising sufficient pressure and temperature to generate afirst reaction mixture comprising a free fatty acid and/or a soap (afatty acid salt), and/or a glyceride (optionally monoacylglycerol (MAG),diacylglycerol (DAG), or triacylglycerol (TAG)),

wherein the thermal hydrolysis reaction is carried out at a temperaturein the range of between about 20° C. to about 600° C., and at a pressureof between about 300 to about 2000 psig (about 20.7 bar to about 137.9bar), and for between about 1 second (sec) to about 3000 minutes (min),or between about 1 min to about 300 min, or between about 5 min to 200min,

and optionally the amount of water in the thermal hydrolysis reaction isbetween about 2:1 water-to-total dissolved solids (TDS) present in themixed lipid feedstock to about 15:1 TDS, or about 10:1 TDS; or betweenabout 1:1 TDS present in the mixed lipid feedstock to about 100:1 TDS,

and optionally a solvent is added to the thermal hydrolysis reaction inan amount of between about 0.01:1 water-to-total dissolved solids (TDS)present in the mixed lipid feedstock to about 100:1 TDS, or about 10:1TDS.

In alternative embodiments, methods and processes as provided hereinfurther comprise an acidification reaction that takes place after orduring (simultaneous with) the thermal hydrolysis step, comprising:

(a) providing an acid or an acid solution or a gas capable of forming anacid when mixed with water, optionally a carbon dioxide (CO₂) or a stackgas; and

(b) combining or mixing the first reaction mixture with the acid or acidsolution or the gas, optionally CO₂, or mixing the first reactionmixture with the acid or acid solution or the gas, optionally CO₂, tohave an acidulation reaction and to generate a second reaction mixture,wherein the first reaction mixture is combined or mixed with the acid oracid solution or the gas, optionally CO₂, for a sufficient amount oftime to acidulate (partially, or substantially all of) the soap in thefirst reaction mixture to generate free fatty acids from the acidulatedsoaps,

and optionally the pH of the acidulation reaction mixture is less thanabout pH 5, or is between about pH 1 to pH 6, or is about pH 1, 2, 3, 4,5 or 6,

and optionally the amount of the gas is sufficient to increase thepressure of the reaction mixture, optionally in a reaction vessel, inwhich the acidulation reaction is being carried out to between about 0and about 2000 psig.

In alternative embodiments, methods and processes as provided hereinfurther comprise mixing the second reaction mixture with an alcohol toform a third reaction mixture comprising fatty acid alkyl esters,wherein optionally the mixing is done under conditions comprisingbetween about 240° C. to about 350° C., or 200° C. to 400° C., and apressure of between about 1400 psi to about 3000 psi,

wherein optionally substantially all of the free fatty acids areesterified to generate fatty acid alkyl esters, optionally, fatty acidmethyl esters,

and optionally the alcohol comprises methanol, ethanol or a mixturethereof.

In alternative embodiments, methods and processes as provided hereinfurther comprise separating, isolating, and/or purifying the free fattyacids and/or the fatty acid alkyl esters into separate fractions.

In alternative embodiments, methods and processes as provided hereinfurther comprise a pre-treatment acidification reaction step fortreating the mixed lipid feedstock before the thermal hydrolysisreaction, wherein the pre-treatment acidification reaction stepcomprises:

(a) (i) providing an acid or an acid solution or a gas capable offorming an acid when mixed with water, optionally a carbon dioxide (CO₂)or a stack gas; and

(ii) combining or mixing the mixed lipid feedstock with the acid or acidsolution or the gas, optionally CO₂, or mixing the mixed lipid feedstockwith the acid or acid solution or the gas, optionally CO₂, to have anacidulation reaction and to generate a pre-treated mixed lipidfeedstock, wherein the mixed lipid feedstock is combined or mixed withthe acid or acid solution or the gas, optionally CO₂, for a sufficientamount of time to acidulate (partially, or substantially all of) thesoap in the mixed lipid feedstock,

and optionally the pH of the pre-treatment acidulation reaction mixtureis less than about pH 5, or is between about pH 1 to pH 6, or is aboutpH 1, 2, 3, 4, 5 or 6,

and optionally the amount of the gas is sufficient to increase thepressure of the pre-treatment reaction mixture, optionally in a reactionvessel, in which the pre-treatment acidulation reaction is being carriedout to between about 0 and about 2000 psig; or

(b) electrolysis (optionally using a hydrogen evolving cathode (HEC)electrolysis unit) of the mixed lipid feedstock for a sufficient amountof time to acidulate (partially, or substantially all of) the soap inthe mixed lipid feedstock.

In alternative embodiments, the natural oil or crude natural oilcomprises a vegetable oil, wherein optionally the vegetable oilcomprises a soybean oil, a canola oil, a rapeseed oil, a corn oil, arice oil, a sunflower oil, a peanut oil, a sesame oil, a palm oil, analgae oil, a jatropha oil, a castor oil, a safflower oil, a grape seedoil or any combination thereof, and optionally the natural oil or crudenatural oil comprises castor oil, and optionally a free fatty acidgenerated is ricinoleic acid (12-hydroxy-9-cis-octadecenoic acid).

In alternative embodiments, the mixed lipid feedstock further comprisesadditional water, a phospholipid and/or an unsaponifiable material.

In alternative embodiments, the acid or acid solution comprises carbonicacid, and optionally the carbonic acid is generated by adding carbondioxide (CO₂) to the first reaction mixture, thereby causing the carbondioxide to react with water in the first reaction mixture to formcarbonic acid, and optionally a source of the carbon dioxide (CO₂)comprises a stack gas or a flue gas, or a gaseous CO₂ emitted from anindustrial process or an oven, a furnace, a boiler, a steam generator, acoal fired power plant, an ethanol plant, a brewery, or an industrialprocess wherein a gaseous waste stream comprising CO₂ is emitted.

In alternative embodiments, the heating and pressurizing of the mixedlipid feedstock is done in a single vessel, or sequential, different,reaction vessels; and optionally the pre-treatment and the thermalhydrolysis are done in a single reaction vessel, and optionally thepre-treatment, the thermal hydrolysis and the post-thermal hydrolysisacidulation are done in the same reaction vessel.

In alternative embodiments, the carbon dioxide is added to the firstreaction mixture, optionally as a liquid, a carbon dioxide gas, or as agaseous flow of carbon dioxide into the reaction vessel.

In alternative embodiments, the soapstock is obtained from the alkalineneutralization of a crude natural oil.

In alternative embodiments, the gums product comprises phospholipids,and optionally the gums product is generated during the degumming of anatural oil.

In alternative embodiments, the mixed lipid feedstock comprises, orfurther comprises, one or more compounds produced as a byproduct fromthe water washing of crude biodiesel, wherein optionally the compoundscomprise soapstock, monoglycerides, diglycerides, triglycerides and/orfatty acid alkyl esters or any combination thereof.

In alternative embodiments, the method is a batch or a continuousprocess.

In alternative embodiments, the heating and pressurizing the mixed lipidfeedstock takes place in conditions comprising: temperature in a rangeof between about 100° C. to 500° C., or 200° C. to 400° C., or 240° C.to 300° C., or at about 260° C.; and/or a pressure of between about 650and 750 psig, between about 750 and 850 psig, between about 850 and 1000psig, between about 1000 and 1500 psig, or between about 1500 psig and1800 psig; and/or for between about 20 and 30 minutes, or between about160 and 180 minutes, or between about 300 minutes and 500 minutes.

In alternative embodiments, the amount of gas is sufficient to increasethe pressure of the reaction mixture, optionally in a reaction vessel,in which the acidulation reaction is being carried out to between about10 and 1000 psig, about 20 to about 600 psig, about 30 to about 500psig, about 40 to about 400 psig, about 50 to about 300 psig, about 60to about 200 psig, about 60 to about 150 psig, about 70 to about 140psig, about 80 to about 120 psig, about 90 to about 110 psig, or about100 psig.

In alternative embodiments, the acidulation reaction is carried out at atemperature in the range of between about 5° C. to about 400° C., e.g.about 10° C. to about 90° C., about 15° C. to about 70° C., about 20° C.to about 60° C., or about 25° C. to about 40° C.

In alternative embodiments, the acid or acid solution comprises anorganic and/or an inorganic acid (a mineral acid), a hydrochloric acid,a sulfuric acid, a formic acid or sodium bisulfate, and optionally whena stack gas comprising N₂O, NO (optionally NO₂), SO_(x) (optionallySO₂), or H₂S is used the N₂O, NO_(x), SO_(x), or H₂S reacts with waterin the acidulation reaction mixture to form equivalent aqueous acidspecies.

In alternative embodiments, after a reaction vessel has reached adesired temperature and pressure to carry out the acidulation step, theresulting reaction mixture is agitated, or otherwise mixed in order tomaximize the contacting of the soaps with the acid, optionally carbonicacid, and optionally the mixture can be agitated using a spinning blademixer, and optionally the mixture is agitated for between about 10minutes to about 200 minutes, e.g. between about 25 minutes to about 150minutes, or between about 20 minutes to about 60 minutes, or about 30minutes.

In alternative embodiments, after the acidulation reaction, andoptionally following an agitation step, the contents of the acidulationreaction, optionally in a reaction vessel, are allowed to settle orpartition allowing for the formation (separation) of a lipid layer andaqueous layer, wherein the lipid layer floats on the top of the aqueouslayer, and optionally the lipid layer comprises free fatty acids and anynon-acidulated soaps, and the aqueous layer comprises water, glycerol,phosphate salts, sodium bicarbonate, sodium carbonate or otherequivalent salts, unsaponifiable material (optionally waxes andsterols), and dissolved carbonic acid.

In alternative embodiments, before or after the reaction products of theacidulation reaction, optionally in a reaction vessel, are allowed tosettle or partition, the reaction products of the acidulation step aretransferred to a separation vessel, optionally a decanter, a settler oran equivalent, or a centrifuge where a lipid phase or component orseparates or partitions out from an aqueous phase or component; or, theacidulation product mixture is not transferred to a separate vessel inorder to separate lipids (the lipid phase or component) from reactionproducts in an aqueous phase or component, and after the lipid phase orcomponent or separates or partitions out from the aqueous phase orcomponent the aqueous layer is drained from the bottom of the reactionvessel and the lipid layer (the lipid phase or component) is recoveredas the reaction product.

In alternative embodiments, methods and processes can further comprisemultiple acidulation reactions, optionally between about 1 and 20additional acidulation reactions, or about 1, 2, 3, 4, 5, 6, 7 or 8 ormore additional acidulation reactions.

The method of any of the preceding claims, wherein after the acidulationreaction the reaction vessel is depressurized, allowing for dissolvedcarbonic acid or other gaseous acid to separate out of the solution asgaseous CO₂, or equivalents, and optionally captured CO₂ is recycled foruse in the further acidulation reactions.

In alternative embodiments, the solvent added to the thermal hydrolysisreaction is a polar (optionally a methanol) or a non-polar (optionally ahexane) solvent.

In alternative embodiments, the thermal hydrolysis reaction and theacidulation reaction take place sequentially; or, the thermal hydrolysisreaction and the acidulation reaction can take place simultaneously as a“one pot” reaction in one reaction vessel.

In alternative embodiments, the lipid phase or component, optionallycomprising unreacted soaps, is transferred to an electrolysis unit(optionally a hydrogen evolving cathode (HEC) electrolysis unit) whereinthe lipid phase is reacted with an anolyte (optionally the anolytecomprises a sodium or potassium sulfate, a sodium or potassium nitrate,or a sodium or potassium chloride) such that the unreacted soapsgenerate free fatty acids, and optionally the electrolysis step convertssubstantially all, or about 90%, 95%, 98% or more of the unreacted soapsto free fatty acids, wherein optionally the anode comprises a mixedmetal oxide (MMO) layer coated onto a stable metal substrate, optionallya titanium.

In alternative embodiments, the lipid phase or component is transferredto an electrolysis unit (optionally a hydrogen evolving cathode (HEC)electrolysis unit) comprising a vessel or suitable container comprisingan anode (e.g., an anode vessel) and a vessel or other suitablecontainer comprising a cathode (an cathode vessel) separated by aselective filtration membrane, optionally a polytetrafluoroethylene(PTFE) membrane, wherein optionally the anode comprises a mixed metaloxide (MMO) layer coated onto a stable metal substrate, optionally atitanium, and optionally the cathode comprises a titanium or a Monelalloy, or any substrate that is stable in a reducing environment.

In alternative embodiments, the aqueous phase or component, or multipleaqueous phases if collected from multiple acidulation reactions, istreated to remove water, wherein optionally the treatment of the aqueousphase or component to remove water is by a drying method, optionallyevaporation via falling film, forced recirculation flashing orequivalent, thereby generating a product comprising sodium bicarbonate,and optionally the product is dried further to generate a sodiumbicarbonate product that is substantially free of any water, optionallyless than about 20% water or less than about 10% water, and optionallythe drying is done using a fluidized bed dryer, a lyophilizer, a spraydryer, or a rotary drum dryer.

In alternative embodiments, the aqueous phase or component, or multipleaqueous phases if collected from multiple acidulation reactions, istreated using a filtration, optionally a membrane filtration system, anano- or microfiltration system or a size-exclusion filtration system,and optionally the filtration is operationally in-line operatingcontinuously with the acidulation step such that aqueous phase generatedin the acidulation reaction (or each acidulation reaction if more thanone acidulation reaction) is treated immediately after or during thepoint at which the aqueous phase is separated from the lipid phase, andoptionally the aqueous phase is collected and treated in a single batch.

In alternative embodiments, soaps and/or other saponifiable materialrejected by the filtration (optionally, soaps and/or other saponifiablematerial that do not pass through a membrane of a filter system) arereturned to the lipid phase for subsequent acidulation reactions,thereby increasing the overall fatty acid yield.

In alternative embodiments, the aqueous phase or component, or multipleaqueous phases if collected from multiple acidulation reactions, istreated with calcium hydroxide (optionally slaked lime) to form acalcium precipitate, optionally a calcium phosphate (Ca_(x)(PO₄)_(x))precipitate. In alternative embodiments, the lime-treated aqueous phaseor component, or multiple aqueous phases if collected from multipleacidulation reactions, is subjected to an oxidation step, optionally aFenton oxidation wherein hydrogen peroxide and Fe²⁺ ions are used tocatalyze OH radical formation.

In alternative embodiments, the aqueous phase or component, or multipleaqueous phases if collected from multiple acidulation reactions, issubjected to electrolysis to recover monovalent ions as a base for avalue added product, wherein electrical current is passed through acathode, the water is reduced, thereby generating hydroxide ions; and asmonovalent ions (optionally sodium or potassium) are pushed across amembrane (separating an anode vessel from a cathode vessel) into thecathode vessel, they react with the generated hydroxide ions to generatea corresponding hydroxide base (optionally a sodium hydroxide or apotassium hydroxide), and optionally the hydroxide base separated out,recovered and/or isolated.

The foregoing has outlined rather broadly the more pertinent andimportant features of the present invention in order that the detaileddescription of the invention that follows may be better understood sothat the present contribution to the art can be more fully appreciated.Additional features of the invention will be described hereinafter whichform the subject of the claims of the invention. It should beappreciated by those skilled in the art that the conception and thespecific embodiment disclosed may be readily utilized as a basis formodifying or designing other structures for carrying out the samepurposes of the present invention. It should also be realized by thoseskilled in the art that such equivalent constructions do not depart fromthe spirit and scope of the invention as set forth in the appendedclaims.

All publications, patents, patent applications cited herein are herebyexpressly incorporated by reference for all purposes.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings set forth herein are illustrative of exemplary embodimentsprovided herein and are not meant to limit the scope of the invention asencompassed by the claims.

FIG. 1 is a flow diagram of an exemplary method as provided hereincomprising generating free fatty acids from a mixed lipid feedstockcomprising soaps, saponifiable material or equivalents thereofcomprising use of thermal hydrolysis followed by acidulation with CO₂.

FIG. 2 is a flow diagram of an exemplary method as provided hereincomprising generating free fatty acids from a mixed lipid feedstockcomprising soaps, saponifiable material or equivalents thereofcomprising use of thermal hydrolysis followed by electrolysis.

FIG. 3 is a flow diagram of an exemplary method as provided hereincomprising generating free fatty acids from a mixed lipid feedstockcomprising soaps, saponifiable material or equivalents thereofcomprising the use of thermal hydrolysis, followed by acidulation withCO₂. and then electrolysis.

FIG. 4 is a flow diagram of an exemplary method as provided hereincomprising generating free fatty acids from a mixed lipid feedstockcomprising soaps, saponifiable material or equivalents thereof, themethod comprising the use of acidulation with an organic and/or mineralacid prior to thermal hydrolysis; thermal hydrolysis is performedfollowed by acidulation with the mineral and/or organic acid.

Like reference symbols in the various drawings indicate like elements.

Reference will now be made in detail to various exemplary embodiments ofthe invention. The following detailed description is provided to givethe reader a better understanding of certain details of aspects andembodiments of the invention, and should not be interpreted as alimitation on the scope of the invention.

DETAILED DESCRIPTION OF THE INVENTION

In alternative embodiments, provided are methods, systems and processesfor the preparation of fatty acids and optionally fatty acidderivatives, e.g. fatty acid alkyl esters, from mixed lipid feedstockscomprising saponifiable material or any triglyceride comprisingmaterial, including byproduct streams of natural oil processing e.g.soapstocks, gums, or mixtures thereof. In alternative embodiments, thefeedstock comprises soapstock obtained from the alkaline neutralizationof a crude natural oil. In alternative embodiments, the feedstockcomprises the gums product (comprising primarily phospholipids)generated during the degumming of a natural oil. In alternativeembodiments, the feedstock comprises a mixture of product streamsgenerated during the processing of a crude natural oil and comprisessoaps as well as saponifiable lipids, e.g. phospholipids. glycerides,e.g. mono-, di-, and/or triglycerides, or any combination thereof.

In alternate embodiments, the mixed lipid feedstock comprises a mixtureof soapstock and monoglycerides produced as a byproduct from the waterwashing of crude biodiesel.

In alternative embodiments, processes and methods as provided herein aremore economical and efficient than currently used approaches for thetreatment of natural oil processing byproducts, e.g., soapstocks andgums, to generate fatty acids, fatty acid derivatives, or othervalue-added products.

In alternative embodiments, a mixed lipid feedstock, e.g. a soapstockcomprising soaps as well as saponifiable material (e.g. glyceridesand/or phospholipids) is reacted by thermal hydrolysis, therebygenerating a product in which substantially all of the free fatty acidsare cleaved from their respective glycerol backbones or phosphategroups. The soaps present in the product stream generated in foregoingthe saponification step are then separated and reacted with an acid inthe acidulation step of the process, in which optionally substantiallyall of the soaps are acidulated to form free fatty acids.

In alternative embodiments, the mixed lipid feedstock comprises crude(unrefined) natural oils, including plant- and animal-derived oils,which are comprised primarily of triacylglycerols (i.e. triglycerides),as well as smaller portions of various lipids including mono- anddiacyl-glycerols, (i.e. mono-glycerides and di-glycerides,respectively), free fatty acids, phospholipids, waxes, and othernon-lipid components including, for example, ketones, aldehydes, andhydrocarbons.

In alternative embodiments, prior to sale for human consumption or forfurther processing, a crude natural oil is refined to remove themajority of the non-triglyceride components. The majority of naturaloils can be refined using a chemical refining process. In the firststage of the chemical refining process, referred to as “degumming”,crude oils are first washed with water to remove the hydratablephospholipids (gums). The resulting product stream separated from theoil during the degumming step is referred to as “gums.” Second, thedegummed oils are subjected to a neutralization step in which thedegummed oil is treated with a strong base, e.g. sodium hydroxide.During the neutralization step, free fatty acids present in the oilreact with the base to form soaps (salts of fatty acids). In alternativeembodiments an additional processing step between the degumming andneutralization step is used in which a small amount of a mineral acid,e.g. phosphoric acid or citric acid, is added to the degummed oil toconvert any non-hydratable phospholipids into hydrated phospholipids.After the neutralization step, the oil is washed to remove the soapsand, if the oil was treated with a mineral acid, the hydratedphospholipids. The resulting product stream separated from the oilduring the neutralization step is referred to as “soapstock.” If the oilis to be sold for human consumption, the degummed, neutralized oil isthen subjected to further processing including, e.g. bleaching anddeodorization steps.

Alternatively, in the production of biodiesel used to practice methodsprovided herein, a lipid mixture is generated as a byproduct. In theproduction of biodiesel, fatty acids are esterified by several meansincluding by enzymatic reaction, acid/base reactions, supercriticalalcohol, and/or ultrasonically. The reaction generates water, which inturn back reacts with the esters to generate monoglycerides and freefatty acids. The removal of these impurities is achieved by water and/orbase washing the crude biodiesel. The washing generates a lipid mixtureproduct of soap, water, and/or monoglycerides, which is regarded as awaste stream in the process of biodiesel refining. This subsequentsoapstock can be utilized in the thermal hydrolysis process providedherein producing high yield free fatty acids as a value added productfor the biodiesel processors.

In alternative embodiments, the configuration of the refinery varies,and soapstock and gums can be either stored separately or combined intoa single storage container. In alternative embodiments, a “mixed lipidfeedstock” refers to any material or composition comprising soaps aswell saponifiable material, i.e. lipids capable of reacting to producesoaps (salts of fatty acids). Saponifiable material in the mixed lipidfeedstock can include, without limitation, glycerides, e.g.mono-glycerides, di-glycerides, or triglycerides, or a combinationthereof, and/or phospholipids. In alternative embodiments, the mixedlipid feedstock is a soapstock. In alternative embodiments, the mixedlipid feedstock comprises soaps and saponifiable lipids e.g. glyceridesand/or phospholipids. In alternative embodiments, the mixed lipidfeedstock is a mixture of soapstocks, comprising soaps, saponifiablematerial, e.g. glycerides and/or phospholipids, obtained during theprocessing of a natural oil. In alternative embodiments, the mixed lipidfeedstock is a soapstock washwater obtained from the processing of acrude natural oil following the neutralization step in the chemicalrefining process. In such embodiments, the washwater can comprise waterand soapstock, wherein the soapstock comprises soaps, glycerides,phospholipids, free fatty acids, and unsaponifiable material e.g. waxesand/or sterols. In alternative embodiments, the soapstock washwater cancomprise between about 1% soapstock to about 100% soapstock, e.g.between about 2% and 80% soapstock, about 3% and 70% soapstock, about 4%and about 60% soapstock, about 5% and about 50% soapstock, about 6% andabout 40% soapstock, about 7% and about 30% soapstock, about 8% andabout 20% soapstock, about 9% and about 15% soapstock, or between about20% and about 12% soapstock, the remaining portion of the soapstockwashwater comprising water.

In alternative embodiments, the composition of the soapstock used as amixed lipid feedstock can vary depending on the crude natural oil fromwhich it was derived. Table 1 shows the composition of varioussoapstocks used to practice methods and processes as provided herein,e.g., as described in U.S. Pat. No. 4,118,407.

TABLE 1 Composition of soapstocks from the refining of various naturaloils Composition Soybean Cottonseed Coconut Palm Kernel Palm Water 57.358.6 66.8 57.8 66.4 Neutral Oil 14.6 13.0 17.4 26.2 8.4 FFA 1.46 0.940.55 0.24 1.25 Unsaponifiable 1.1 1.4 0.85 0.38 0.2 Soap 14.2 17.5 14.414.2 23.8 Phosphatide 11.34 8.56 0 0 0 Phosphorus 0.8 0.38 0.16 0 0Total FFA 23.7 27.6 27.3 38.1 21.9 pH 9.5 9.5 9.2 9.2 10.8

Other mixed lipid feedstocks suitable for use in methods and processesas provided herein comprises tall oil soaps. Tall oil soaps aregenerated via the alkaline pulping of wood in the Kraft process. Thealkaline pulping of wood using the Kraft process results in theproduction of black liquor, comprising the majority of the non-cellulosecomponents of the wood. These products include hemicelluloses, lignin,and various salts of carboxylic acids including rosin salts and soaps(salts of fatty acids). After the black liquor is concentrated usingmultiple effect evaporators, it is allowed to settle or is centrifuged.As the concentrated black liquor settles, the soaps float to the surfacewhere they are skimmed and removed. The skimmed product (referred to asblack liquor soaps or tall oil soaps) can be used as a feedstock invarious embodiments of processes and methods as provided herein.

In alternative embodiments, the mixed lipid feedstock used to practicemethods and processes as provided herein comprises a saponified crudenatural oil, e.g. a saponified vegetable oil. In alternativeembodiments, the mixed lipid feed feedstock is a saponified castor oil,i.e. a composition comprising soaps derived from mixing a base with acastor oil, the saponifiable content in the castor oil, e.g. glycerides,and phospholipids, having been converted to soaps. The majority of thefatty acid content in castor oil (e.g. between 80 to about 95% of thefatty acid content) is ricinoleic acid (12-hydroxy-9-cis-octadecenoicacid). In alternative embodiments, provided are methods or processes forgenerating ricinoleic acid by thermal hydrolysis, acidulating thesaponified castor oil to generate free fatty acids, and then separatingor isolating ricinoleic acid from the generated free fatty acids.

Alternative embodiments of the methods and processes are described ingreater detail below.

Thermal Hydrolysis

In alternative embodiments, in thermal hydrolysis processes as providedherein, the mixed lipid feedstock is hydrolyzed and the reaction isdriven by heat and pressure. The reaction mechanism includes thehydroxyl ion attacking the carbonyl group(s), or ester(s), present inmixed lipid feedstocks in the form of triglycerides, and/orphospholipids. When full reaction proceeds, the process yields fattyacids, glycerol, and other non-TFA solids due to the inherent nature ofsoapstock.

In alternative embodiments, the first stage of the process is a thermalhydrolysis reaction with a mixed lipid feedstock. In alternativeembodiments, the thermal hydrolysis reaction can take place in anysuitable reaction vessel known in the art. In alternative embodiments,the reaction can be a batch or continuous process, depending on thedesired throughput of material from the reaction. In alternativeembodiments, the process involves adding a mixed lipid feedstock to areactor where thermal hydrolysis will occur.

In alternative embodiments, the thermal hydrolysis reaction is carriedout at a temperature in the range of between about 20° C. to about 600°C., or in a range of between about 100° C. to 500° C., or about 200° C.to 400° C., or about 240° C. to 300° C., or at about 260° C. Inalternative embodiments, the thermal hydrolysis reaction is carried outat a pressure of between about 500 to 2000 psig, between about 650 and750 psig, between about 750 and 850 psig, between about 850 and 1000psig, between about 1000 and 1500 psig, or between about 1500 psig and1800 psig. In alternative embodiments, the thermal hydrolysis reactionis carried out at ambient pressure. In alternative embodiments, the timeallotted for the reaction to occur is between about 1 minute and 300minutes, e.g. between about 20 and 30 minutes, or between about 160 and180 minutes, or between about 300 minutes and 500 minutes. Inalternative embodiments, the amount of water in the thermal hydrolysisreaction is between about 2:1 water-to-total dissolved solids (TDS)present in the feedstock to about 15:1, e.g. about 10:1.

Acidulation of Soaps:

In alternative embodiments, the fatty acids, or the reaction productgenerated during the thermal hydrolysis step of the process is subjectedto an acidulation step in which most, or substantially all, of theremaining soaps are acidulated to generate free fatty acids. The soapsare acidulated by mixing them, in any suitable reaction vessel, e.g. thesame reaction vessel that was used in the thermal hydrolysis step, withan acid to form an acidulation reaction mixture.

In alternative embodiments, the acid is either an organic or inorganicacid, e.g. carbonic acid. In alternative embodiments, carbonic acid isgenerated by mixing CO₂ with the thermal hydrolysis reaction product,wherein the CO₂ reacts with the water (present in the thermal hydrolysisreaction product) to form carbonic acid. In alternative embodiments, theCO₂ is a liquid or a gas or a combination thereof. In an exemplaryembodiment, when the CO₂ is a gas, the CO₂ is then piped or otherwisedirected into the reaction vessel wherein the CO₂ reacts with the waterpresent in the thermal hydrolysis reaction product to form carbonicacid. Once formed, the carbonic acid reacts with the soaps, therebyacidulating them and generating free fatty acids and a correspondingsalt, e.g. sodium bicarbonate.

The amount of CO₂ used in the acidulation step of alternativeembodiments of the process can vary depending on, for example, ambienttemperature and pressure conditions, but is generally sufficient toincrease the pressure of the reaction vessel in which the acidulationreaction is being carried out to between about 0 and about 2000 psig,e.g. between about 10 and 1000 psig, about 20 to about 600 psig, about30 to about 500 psig, about 40 to about 400 psig, about 50 to about 300psig, about 60 to about 200 psig, about 60 to about 150 psig, about 70to about 140 psig, about 80 to about 120 psig, about 90 to about 110psig, or about 100 psig. In alternative embodiments, the acidulationreaction is carried out at a temperature in the range of between about5° C. to about 400° C., e.g. about 10° C. to about 90° C., about 15° C.to about 70° C., about 20° C. to about 60° C., or about 25° C. to about40° C.

In alternative embodiments, the source of the CO₂ used in theacidulation step is a “stack gas” or “flue gas” (used interchangeablyherein and referred to as “stack gas”) other source of gaseous CO₂emitted from an industrial process or any oven, furnace, boiler, steamgenerator or the like, e.g. from a coal fired power plant, ethanolplant, brewery, or any other industrial process wherein a gaseous wastestream comprising CO₂ is emitted.

In alternative embodiments, the stack gas is piped or otherwisetransferred from the emission source to the vessel in which theacidulation reaction is carried out. In alternative embodiments, thestack gas can comprise gaseous CO₂ and possibly other products dependingon the filtration or other purification steps that the stack gas wassubjected to prior to being transferred to the acidulation reactor. Theexact composition of the stack gas will vary depending on the emissionsource and post-combustion processing steps but is generally comprisedprimarily of CO₂ (e.g. about 60% or more CO₂), nitrogenous products(e.g. N₂O and NO₂), sulfur dioxide (SO₂), hydrogen sulfide (H₂S), watervapor and possibly other products.

In alternative embodiments wherein a stack gas is used as the CO₂source, other products in the stack gas, e.g. N₂O, NO₂, SO₂, H₂S or thelike can react with the water in the acidulation reaction mixture toform their equivalent aqueous acid species (e.g., SO₂ would react withthe water to generate sulfuric acid). The generation of additional acidproducts in the reaction mixture can serve to increase the reactionefficiency and reduce the total amount of time required to perform theacidulation reaction. As such, the use of a stack gas “waste stream” maybe beneficial in the process, representing an opportunity to utilize awaste stream from one industrial process to benefit another industrialprocess (which might otherwise require expensive processing steps priorto being emitted) as an input for the present process. The processtherefore is a means of diverting what would otherwise be anenvironmental pollutant to an input stream of a separate industrialprocess.

In alternate embodiments, the CO₂ can be liquid from a bulk tank ortruck. Other products may optionally be added to the acidulationreaction mixture e.g. organic or inorganic acids, e.g. formic acid orsodium bisulfate. The addition of additional acids can be useful intailoring the ash profile of the resulting acidulation product mixture(the mixture of products resulting from the acidulation reaction) suchthat certain end products can be used as, e.g. a fertilizer. Theoptional addition of additional acids can serve to increase the reactionefficiency by acidulating soaps that were not acidulated by the carbonicacid.

In alternative embodiments, the desired pH of the acidulation reactionmixture is less than about pH 5, or is between about pH 1 to pH 6, or isabout pH 1, 2, 3, 4, 5 or 6. In alternative embodiments, the amount ofCO₂ and optional other acids (e.g. from stack gas) added to theacidulation reaction mixture is sufficient to reduce the pH of themixture to below 5 or about 2 or 3.

In alternative embodiments, flowing the addition of the CO₂ (or stackgas, or carbonated water) and optional other acids to the saponification(thermal hydrolysis) reaction product and after the reaction vessel hasreached the desired temperature and pressure to carry out theacidulation step, the resulting reaction mixture is agitated, orotherwise mixed in order to maximize the contacting of the soaps withthe carbonic acid (generated once CO₂ reacts with the water present inthe saponification reaction mixture). The mixture can be agitated usingany suitable method known in the art, e.g. a spinning blade mixer. Inalternative embodiments, the mixture is agitated for between about 10minutes to about 200 minutes, e.g. between about 25 minutes to about 150minutes, or between about 20 minutes to about 60 minutes, or about 30minutes.

In alternative embodiments, following the agitation step, the contentsof the acidulation reaction vessel are allowed to settle, allowing forthe formation of a lipid layer and aqueous layer. The lipid layer floatson the top of the aqueous layer. In alternative embodiments, the lipidlayer comprises free fatty acids and any non-acidulated soaps, and theaqueous layer comprises, for example, water, glycerol, phosphate salts,sodium bicarbonate, smaller amounts of sodium carbonate (or otherequivalent salts), unsaponifiable material e.g. waxes and sterols, anddissolved carbonic acid. In alternative embodiments, the lipid layercomprising the free fatty acids generated in the acidulation reaction isseparated from the remaining reaction products. The separation techniqueused can be any suitable separation technique known in the art. Inalternative embodiments, the reaction products of the acidulation stepare transferred to a separation vessel, e.g. a decanter wherein themixture is allowed to settle and allowed to separate, forming an aqueousphase and a “lipid” phase comprising the free fatty acids which floatson top of the aqueous phase. In alternative embodiments, the decantationprocedure results in the formation of separate lipid and aqueous phasesin approximately 1 hour or less, depending on the configuration of thereaction vessel. Other separation techniques, e.g. centrifugation, mayalso be used in accordance with embodiments as provided herein. Incertain embodiments, the acidulation product mixture is not transferredto a separate vessel in order to separate the lipids from the remainingreaction products. In such embodiments, the aqueous layer is drainedfrom the bottom of the reaction vessel and the lipid layer is recoveredas the reaction product.

In alternative embodiments, the reaction products generated during theacidulation reaction are transferred to the separation unit in such away that the loss of any gaseous CO₂ is minimized, e.g. via the use of aliquid level control feedback or other suitable method.

In certain embodiments, after the acidulation reaction, the reactionvessel is depressurized, allowing for the dissolved carbonic acid toseparate out of the solution as gaseous CO₂. In such embodiments, thecaptured CO₂ is recycled for use in the acidulation step.

In alternative embodiments, the process comprises multiple acidulationreactions e.g. between about 1 and 20, or about 1, 2, 3, 4, 5, 6, 7, 8,or 9 or more acidulation reactions. In such embodiments, following thefirst acidulation reaction as described above, the reaction vessel isdepressurized and the CO₂ is captured and recycled. The lipid layer isthen separated or otherwise removed from the aqueous layer, and water isadded into the reaction vessel containing the lipid layer. CO₂ is thenadded to the reaction vessel until the desired pressure is reached asdescribed above. The reaction vessel is then heated and agitated aspreviously described and allowed to settle. The resulting lipid layer isthen separated or otherwise removed from the aqueous layer as previouslydescribed. The resulting lipid layer is then separated or otherwiseremoved and can optionally be subjected to additional acidulationreactions as previously described, wherein additional water and CO₂ isadded and the resulting mixture agitated at the desired temperature andpressure and the resulting lipid layer is separated or otherwise removedfrom the aqueous layer. The number of acidulation reactions in theprocess can vary depending on the desired free fatty acid yield andprocess economics. In certain embodiments, the number of acidulationreactions is sufficient to acidulate substantially all of the soapspresent in the thermal hydrolysis product mixture, e.g. lto 8acidulation reactions, e.g. 2 acidulation reactions.

In alternate embodiments, following the first acidulation reaction asdescribed above, the reaction vessel is not depressurized and the CO₂ isallowed to remain in the pressure vessel. Instead, the aqueous layer issubsequently drained from the bottom of the reactor and recycled to beused in subsequent acidulation reactions where the CO₂ remainspressurized in the vessel. In alternative embodiments, a salt, e.g.sodium chloride or other equivalent salt, is added to the productmixture following an acidulation reaction. The addition of NaCl orequivalent salt to the acidulation reaction product increases the ionicstrength of the product mixture and prevents the lipid layer fromemulsifying with the aqueous layer. In certain embodiments, the processcomprises one or more acidulation reactions and the salt, e.g. NaCl, isadded to the product mixture generated by the first acidulationreaction. In certain embodiments, the process comprises two or moreacidulation reactions, e.g. six acidulation reactions, and the salt isadded to the product mixture generated by the third acidulationreaction.

The acidulation reaction, or multiple acidulation reactions, can takeplace in any suitable reaction vessel known in the art. In alternativeembodiments, the reaction can be a batch or continuous process,depending on the desired throughput of material from the reaction. Inembodiments of the process comprising multiple acidulation reactions,the multiple acidulation reactions can take place in the same reactionvessel or in separate reaction vessels. In embodiments comprisingmultiple acidulation reactions taking place in multiple reactionvessels, the lipid layer generated during each acidulation reaction isseparated or otherwise removed from the corresponding aqueous layer andtransferred to a separate reaction vessel wherein the lipid layer ismixed with water and CO₂ and the resulting mixture is agitated for thedesired period under the desired temperature and pressure conditions andallowed to settle in order to generate a new lipid layer.

In alternative embodiments, the separated free fatty acids generated inthe acidulation reaction are subjected to further processing steps. Inalternative embodiments, the free fatty acids are further separated bytheir carbon chain length, i.e. the number of carbon atoms contained inthe aliphatic tail portion of the free fatty acid, which can comprise,in alternative embodiments, between 4 and 28 carbon atoms. Inalternative embodiments, the free fatty acids are separated by theirsaturation. In alternative embodiments, the saturated free fatty acidsare separated from the unsaturated free fatty acids. In alternativeembodiments, the separated free fatty acids are separated intoshort-chain fatty acids (aliphatic tail length of fewer than 6 carbonatoms), medium-chain fatty acids (aliphatic tail lengths of between 6and 12 carbon atoms), long-chain fatty acids (aliphatic tail length ofbetween 13 and 21 carbon atoms), and very long-chain fatty acids(aliphatic tail length of 22 or more carbon atoms). In alternativeembodiments, the separated free fatty acids are separated intoindividual fatty acids streams based on the length (number of carbonatoms) of their aliphatic tails.

In alternative embodiments, the separated free fatty acids can befurther separated into distinct cuts, based on their aliphatic taillength and/or saturation, using any suitable technique known in the art,e.g. ion exchange, continuous ion exchange, chromatography, continuouschromatography or the like.

In alternative embodiments, the thermal hydrolysis reaction and theacidulation reaction take place sequentially; or, the thermal hydrolysisreaction and the acidulation reaction can take place simultaneously,e.g., as in a “one pot” reaction in one reaction vessel.

Electrolysis of Lipid Phase from Acidulation Reaction:

In alternative embodiments, the lipid phase having been separated in theforegoing acidulation reaction(s) comprises a small percentage ofunreacted soaps, for example, soaps that were not acidulated to generatefree fatty acids, e.g., between about 5 wt % and 30 wt %, or about 10 wt% of the lipid phase. In order to increase the overall efficiency of theprocess, alternative embodiments of the process comprise an electrolysisstep wherein the lipid phase comprising a small amount of unreactedsoaps is transferred to an electrolysis unit wherein the soaps in thelipid are reacted with an anolyte to generate free fatty acids. Inalternative embodiments, the addition of the electrolysis step convertssubstantially all, e.g., 90%, 95%, 98% or more of the unreacted soaps tofree fatty acids.

In alternative embodiments comprising the electrolysis step, the lipidlayer from the acidulation reaction(s) is transferred to an electrolysisunit (e.g. a hydrogen evolving cathode (HEC) electrolysis unit)comprising a vessel or suitable container comprising an anode (the anodevessel) and a vessel or other suitable container comprising a cathode(the cathode vessel) separated by a selective filtration membrane, e.g.a polytetrafluoroethylene (PTFE) membrane. In alternative embodiments,the anode is comprised of a mixed metal oxide (MMO) layer coated onto astable metal substrate, e.g. titanium. In alternative embodiments, thecathode can be, for example, titanium or a Monel alloy (a nickel alloyprimarily composed of nickel (up to 67%) and copper), or any othersubstrate that is stable in a reducing environment.

In alternative embodiments, a solution comprising an anolyte is added tothe anode vessel. In alternative embodiments the anolyte is a sodiumand/or potassium salt, e.g. sodium or potassium sulfate (forillustrative purposes, sodium sulfate is the anolyte in the remainingdescription of the electrolysis step, although those skilled in the artwould appreciate that an equivalent anolyte such as potassium sulfatemay be substituted in the process). Simultaneously, the cathode vesselis filled with a catholyte, e.g. sodium hydroxide. In alternativeembodiments, a current is passed through the electrolysis unit resultingin the oxidation of the sodium sulfate, thereby generating sodium ionsand sodium bisulfate. The current also can serve to oxidize the water,generating hydrogen ions. The generated sodium ions are pushed acrossthe electrolysis membrane and the generated sodium bisulfate results ina reduction of the pH of the anolyte solution to, e.g. about 3. Once thepH has reached a suitable level, e.g. about 3, a portion of theseparated lipid from the acidulation step can be introduced into thevessel with the anolyte solution wherein any unreacted soaps in thelipid layer react with the sodium bisulfate to generate free fatty acidsand sodium sulfate. The generated free fatty acids can be separated fromthe anode vessel by any suitable method in the art, e.g. through a pipeat the top of the anode vessel and into separate side tank. Thegenerated sodium sulfate acts as the regenerated anolyte which, afterthe fatty acids have been removed from the anode vessel, and can beoxidized by passing a current through the anode. As such, theelectrolysis unit operates in a semi-continuous fashion, wherein sodiumsulfate is oxidized to generate sodium bisulfate, thereby lowering thepH of the anolyte solution. In alternative embodiments, once the pH hasreached a suitable level, e.g. about 3 additional lipid material fromthe acidulation reaction step is added, and the soaps present in thelipid material react with the sodium bisulfate to generate free fattyacids and sodium sulfate.

In alternative embodiments, as the electrical current is passed throughthe cathode, the water is reduced, thereby generating hydroxide ions. Asthe sodium ions are pushed across the membrane from the anode vesselinto the cathode vessel, they react with the generated hydroxide ions togenerate sodium hydroxide. In alternative embodiments, the startingconcentration of the catholyte (sodium hydroxide) can be about 30 wt %.As additional sodium hydroxide can be generated (from the sodium ionsmoving across the membrane and into the cathode and reacting with thehydroxide ions), the concentration of sodium hydroxide can be increasedto, e.g. about 33 wt %, before some of the sodium hydroxide is removedto bring the concentration back down to its original concentration, e.g.30 wt %. The generated sodium hydroxide solution comprising sodiumhydroxide and water can be recycled, or sold as a value added product.

In alternative embodiments, the electrolysis unit is a hydrogen evolvingcathode (HEC) unit with a current density in the range of about 1-10kA/m². In alternative embodiments, the voltage of the individual cellsof the unit can be in the range of between about 3 and 15 volts. Inalternative embodiments, the unit comprises holding tanks for theanolyte and catholyte for electrolyte balancing as the process iscarried out. In alternative embodiments, the holding tank of thecatholyte also serves as the additional tank for the lipid product, aswell as a decanter for separating fatty acids generated in the process.In alternative embodiments, upon startup of the electrolysis unit, thesodium sulfate anolyte is electrolyzed, causing the pH of the anolytesolution to drop from, e.g. about 7 to about 3 to 3.5, and thetemperature of the anode vessel is increased to between about 40 to 90°C., or above the melting point of the lipid solution entering the anode.In alternative embodiments, the lipid product is added to the anolytesolution until the pH increases to, e.g. about 4.5, after which pointthe addition of the lipid product is halted. In alternative embodiments,once the anolyte is electrolyzed, it contacts the soaps, which float inthe holding tank/decanter due to limited solubility in the anolyte. Oncethe pH in the anolyte solution is reduced to 3-3.5, the circulating pumphalts and fatty acids can be decanted from the anolyte for downstreamprocessing.

In alternative embodiments, the foregoing electrolysis procedure is usedas a total replacement of the acidulation reaction comprisingacidulating soaps using carbonic acid. In such embodiments, the thermalhydrolysis product mixture generated in the thermal hydrolysis reactionis subjected to electrolysis as described above, wherein the productentering the anode vessel of the electrolysis unit is the thermalhydrolysis product mixture rather than the lipid layer separated fromthe acidulation product mixture.

Treatment of Aqueous Phase from Acidulation Reaction:

Evaporation/Drying

In alternative embodiments, the aqueous phase(s) generated in the one ormore acidulation reactions is subjected to one or more processing stepsin order to recover desirable reaction products that remain in theaqueous phase of the acidulation reaction products and/or to treat theaqueous phase such that the resulting product meets or exceeds relevantregulatory standards relating to animal feed additives.

In alternative embodiments, the aqueous phase, or multiple aqueousphases (i.e. collected from acidulation reactions) is treated to removewater, e.g. by any suitable drying method (e.g. evaporation via fallingfilm, forced recirculation flashing, or any other suitable method) knownin the art, thereby generating a product comprising sodium bicarbonate.Care must be taken so as not to convert sodium bicarbonate to sodiumcarbonate via thermal degradation, so evaporation temperature should beconducted below about 60° C. and should be conducted under a vacuum.

In alternative embodiments, once a majority of the water has beenremoved from the aqueous stream(s), the resulting product can be driedfurther to generate a sodium bicarbonate product that is substantiallyfree of any water, e.g. less than about 20% water or less than about 10%water. Suitable apparatuses for creating a substantially dry sodiumbicarbonate product include fluidized bed dryers, lyophilizers, spraydryers, and rotary drum dryers. The generated dried sodium bicarbonateproduct can be used in any application that utilizes a crude sodiumbicarbonate stream, e.g. as an animal feed additive.

Filtration

In alternative embodiments, the aqueous phase(s) generated in the one ormore acidulation reactions is subjected to one or more processing stepsin order to recover desirable reaction products that remain in theaqueous phase of the acidulation reaction products and/or to treat theaqueous phase such that the resulting product meets or exceeds relevantregulatory standards relating to wastewater. In alternative embodiments,the aqueous phase(s) generated during one or more acidulation reactionscan comprise various organic molecules and salts in addition to water.The exact composition of the aqueous phase(s) will vary depending on thefeedstock used in the process, as well as other process variables, e.g.the reaction conditions, separation technique to separate the lipidphase from the aqueous phase during the acidulation process, etc. Inalternative embodiments, the aqueous phase(s) may include, in additionto water: sodium bicarbonate (or equivalent salt), glycerol, phosphates,cholines, ethanolamines, sodium sulfate (or equivalent salt), inositol,unreacted saponifiable material, e.g. soaps and/or glycerides, residual(small amounts of) free fatty acids, other organic or inorganiccompounds, or any combination thereof.

The composition of an exemplary aqueous phase generated in theacidulation step comprising 6 acidulation reactions, wherein thefeedstock of the process is a soapstock obtained from the processing ofa crude soybean oil, is described below:

Water 92.8% Sodium sulfate 1.4% Glycerin 0.79% Choline 0.06%Ethanolamine 0.02% Inositol 0.05% Phosphate 0.12% Sodium bicarbonate4.72%

In alternative embodiments, the aqueous phase(s) may be treated usingfiltration, e.g. a size-exclusion filtration system. In alternativeembodiments, the filtration step may be operationally in-line (i.e.continuously) with the acidulation step such that aqueous phasegenerated in each acidulation reaction (if the embodiment comprises morethan one acidulation reaction) is treated immediately after or duringthe point at which the aqueous phase is separated from the lipid phase.In other embodiments, the aqueous phases may be collected and treated ina single batch.

In alternative embodiments, wherein the process comprises multipleacidulation reactions, the aqueous phase generated in each of theacidulation reactions is continuously pumped through a filtrationmechanism, e.g. a nano- or microfiltration system or other appropriatemembrane filtration system which may be selected from any of the knownnano-, micro- or other appropriate size-exclusion filtration mechanismsor systems known in the art. In alternative embodiments, the size of thepores of the filter allows for the rejection (i.e. allows the particlesto pass through the membrane) of certain particles, e.g. soaps and/orphosphates, and retains (i.e. does not allow the particles to passthrough the membrane) the sodium bicarbonate (or other equivalent salt).In alternative embodiments, the particles that pass through the membraneof the filter have a molecular weight less than the molecular weight ofsodium palmitate, e.g. sodium bicarbonate, sodium phosphates, etc. Inalternative embodiments, rejected particles are sodium (or otherequivalent) soaps, e.g. sodium palmitate, sodium oleate, etc. Inalternative embodiments, the filtration system provides for a moreefficient process in that the soaps and/or other saponifiable materialrejected by the membrane of the filter are returned to the lipid phasefor subsequent acidulation reactions, thereby increasing the overallfatty acid yield of the process.

In alternative embodiments, the addition of a filtration step in theprocess serves to drive the acidulation reaction to completion byremoving the sodium bicarbonate (or other equivalent salt) from theacidulation product. Sodium bicarbonate can “back-react” with the fattyacids generated in the acidulation step, wherein some of the fatty acidsreact with the sodium bicarbonate to generate soaps, thereby loweringthe overall fatty acid yield of the process. By removing the generatedsodium bicarbonate from the acidulation products, the opportunity forback-reacting with the sodium bicarbonate is diminished and the fattyacid yield of the process is increased.

In alternative embodiments, the filtration step is carried out in a pHrange of between about 6 and 11 and a pressure of between about 50 and800 psi, while maintaining a temperature of between about 23 and 100° C.In alternative embodiments, the pH of the acidulation product solutionon which the filtration step is carried out varies depending on theamount of sodium bicarbonate in the solution. As the sodium bicarbonateis removed, e.g. via filtration, the pH drops and becomes increasinglyacidic, thereby driving the acidulation reaction to completion. Inalternative embodiments, the aqueous phase of the acidulationreaction(s) is pumped through the filter at a range of between about 1and 100 gallons per minute. In alternative embodiments, the size of thepores in the filter membrane has a molecular weight cutoff (MWCO) ofbetween about 100-250 Daltons.

In alternative embodiments, the retained portion of the aqueous phasecomprising the sodium bicarbonate (or other equivalent salt if sodiumhydroxide was not used in the saponification reaction step) is thensubjected to a concentration step using, for example, reverse osmosis(RO). In alternative embodiments, the conditions for the RO step aresimilar to those of the filtration step, i.e. a pH in the range ofbetween about pH 6 and pH 11, a pressure of between about 50 psi and 800psi, while maintaining a temperature of between about 23° C. and 100° C.In alternative embodiments, the concentrated sodium hydroxide can bediscarded or sold, increasing the overall efficiency of the process. Inalternative embodiments, the water produced in the RO step is suitablypure to be recycled within the acidulation step, thereby increasing theefficiency of the process and reducing total water consumption.

Lime Treatment and Oxidation of Organics

In alternative embodiments, the aqueous phase generated in theacidulation reaction, or multiple acidulation reactions, is collectedand contacted with calcium hydroxide, i.e. slaked lime. The amount oflime added to the aqueous phase is generally an amount sufficient toincrease the pH of the solution to about 11. The lime-treated aqueousphase is allowed to react for a period of between about 1 and 24 hours.During the reaction time, various precipitates form and the pH of thesolution increases to about 12 or 13.

In the same lime-contacting step described above, various calciumprecipitates are formed when they react with various components in theaqueous phase. These precipitates can include, for example, variouscalcium phosphates (i.e. Ca_(x)(PO₄)_(x)). Other components of thelime-treated aqueous phase can include, for example, those products thatwere present in the recovered aqueous phase of the one or moreacidulation reactions that did not react with the lime, e.g. glycerol,ethanolamines, choline, other organics, or any combination thereof.

In order to satisfy the Biochemical Oxygen Demand requirements forconventional wastewater treatment facilities, in alternativeembodiments, the lime-treated aqueous phase product may be subjected toan oxidation step in which the organics present in the solution, e.g.phosphorous, glycerin, and other organics are fully oxidized intogaseous products that precipitate out of solution. In alternativeembodiments, the lime-treated aqueous phase is subjected to Fentonoxidation wherein hydrogen peroxide and Fe²⁺ ions are used to catalyzeOH radical formation. In alternative embodiments, the Fenton oxidationstep is carried out by adding between about 1 and 10 grams of hydrogenperoxide per liter of aqueous phase liquid and between about 0.1 and 1.0mol Fe²⁺ per mol of hydrogen peroxide to the lime-treated aqueous phase.The resulting mixture is then allowed to react for between about 1 and24 hours at a temperature of between about 20-50° C. Once the hydrogenperoxide and Fe²⁺ are added to the lime-treated aqueous phase, the pHwill drop rapidly to between about 3 and 9, e.g. less than pH 7. The pHthen rises slowly as the organics are gasified and leaves the solution.The reaction is considered complete when the rate of change in the pH ofthe solution is less than about 0.1 units/hour. UV oxidation canoptionally be used in combination with Fenton oxidation.

In alternative embodiments, following the oxidation step, the solutionis then contacted with fresh lime to precipitate any unbound phosphorusand other acidic species. The conditions for the second lime treatmentstep are identical to those of the first lime treatment step.

Electrolysis of Aqueous Phase

In alternative embodiments, the aqueous phase is subject to electrolysisto recover monovalent ions as a base for a value added product. Inalternative embodiments, as the electrical current is passed through thecathode, the water is reduced, thereby generating hydroxide ions. As themonovalent ions, e.g. sodium or potassium, are pushed across themembrane from the anode vessel into the cathode vessel, they react withthe generated hydroxide ions to generate the corresponding hydroxidebase, e.g. sodium hydroxide or potassium hydroxide, which can berecovered and sold as a value added product.

The invention will be further described with reference to the examplesdescribed herein; however, it is to be understood that the invention andembodiments as provided herein are not limited to such examples.

EXAMPLES Example 1: Thermal Hydrolysis and Acidulation of Mixed LipidFeedstock

This Example Describes an Exemplary Protocol of the Invention:

A mixed lipid feedstock comprised of soapstock, glycerides, andphospholipids was obtained from an oil refining facility. The mixedlipid feedstock was added to a vessel and subject to thermal hydrolysisto free the fatty acids from their glycerol backbones and phosphategroups. The lipid product resulting from the thermal hydrolysis reactionwas then subjected to a first acidulation reaction wherein CO₂ wasintroduced into the reaction vessel comprising the lipid product. TheCO₂ reacted with the water in the lipid product to form carbonic acidand acidulated soaps, thereby generating an acidulation reaction productcomprising a first lipid layer of free fatty acids and an aqueous layercomprising water glycerol, sodium bicarbonate, unsaponifiable material,e.g. waxes and sterols, dissolved carbonic acid, and phosphate salts.

Feedstock Description:

The feedstock used in the present example was a mixed soapstock obtainedfrom a natural oil refinery. Water was added to the mixed feedstock toensure a ratio of 5:1 water-to-total dissolved solids (TDS), orwater:TDS. The mixture was then added to an autoclave (e.g., a Parr)reactor where thermal hydrolysis was performed. The total mass added tothe 2 L autoclave (e.g., Parr) reactor was 1.4 kg of feedstock materialand water.

Composition of Feedstock:

55 gallons soy soapstock (Archer Daniels Midland, Chicago, Ill.);Makeup: 24.7 wt % TDS (Soaps, saponifiable material, and unsaponifiablematerial), 15.9 wt % free fatty acids (64% dry TFA based on TDS) and46.14 wt % water.

Thermal Hydrolysis Reaction:

Thermal Hydrolysis Reaction:

Nitrogen gas was used to purge the reactor of air once the feedstock wasadded. This was repeated 5 times to guarantee the air had been purgedfrom the reactor. The reactor temperature was set to 270° C. whichallowed thermal hydrolysis to occur. Agitation was set to approximately60 rpm to allow minimal movement. The temperature was held at 270° C.for 30 minutes. The reactor was then allowed to cool to 90° C. and apost-thermal hydrolysis sample was acquired from the bottom of thereactor.

Acidulation Reaction:

Acidulation Reaction:

After the thermal hydrolysis reaction, CO₂ was slowly introduced, e.g.,over a period of about 8, 9 or 10 minutes or more, into the sealedreaction vessel through a port located near the bottom of the vessel.CO₂ was continually added to the reaction vessel until the pressureinside the vessel reached 300 psig. The reaction vessel was maintainedat a temperature of 90° C. and agitated using a spinning blade mixerspinning at 400 rpms for a period of 30 minutes. After 30 minutes, thecontents of the reaction vessel were allowed to settle for 10 minutes.During settling, a lipid layer and an aqueous layer formed and the lipidlayer floated on top of the aqueous layer. The aqueous layer was drainedfrom the bottom of the reaction vessel.

Second Acidulation Reaction:

After the aqueous layer was removed following the first acidulationreaction, the reaction vessel was not depressurized. The contents in thereaction vessel were agitated using the spinning blade mixer as 95 partsfresh water (based on 100 parts of the first aqueous fraction) wassimultaneously introduced through the top of the reaction vessel. Thereaction vessel was maintained at a temperature of 90° C. and agitatedusing the spinning blade mixer at 400 rpms for a period of 30 minutes.After 30 minutes, the contents of the reaction vessel were allowed tosettle for 10 minutes. During settling, a lipid layer and an aqueouslayer formed and the lipid layer floated on top of the aqueous layer.The aqueous layer was drained from the bottom of the reaction vessel.

Analysis of FFA Content and FFA Profile:

Following the second acidulation reaction, a sample of the hexane layercomprising the free fatty acids (FFAs) was removed from the reactionvessel for analysis. First, the hexane was removed from the sample.Using acid titration, it was determined that the fatty acid content ofthe sample was 91 wt % FFA (normalized based on FFA & soap). Theremainder of the sample was comprised of soaps and variousunsaponifiable material. The fatty acid profile of the sample is shownis Table 2.

TABLE 2 Fatty acid profile of sample C16 C18 Other FFAs Monos, di-acids,etc. 19% 79% <1% ≤1%

Example 2: Electrolysis of Lipid Phase from Acidulation Reaction

Materials:

Two one liter working solutions in 2 L glass beakers with stirbars on1000 W hotplates being recirculated by constant flow rate peristalticpumps @ 60° C. (anolyte is saturated aqueous sodium sulfate andcatholyte is 10 wt % sodium hydroxide); 5 cm² NAFION 115TH membrane, PVCbody and tubing, 6″×1″ DSA, 6″×1″ Monel 400 cathode.

Using 0-30 V 0-20 A DC power supply, turn power supply on to provideconstant amperage of 3 A to electrodes in PVC system. Pump anolyte andcatholyte around with their respective peristaltic pumps at 750 mL/minand heat both to 60° C. Reduce anolyte (side with Na₂SO₄ solution) pH toabout 3 to 3.5 before slowly adding enough saponified soapstock toincrease pH of anolyte to 5. Stop addition of saponified soapstock andallow electrochemical cell to reduce anolyte pH back to about 3 to 3.5before adding more saponified soapstock. Halt cycle once 60 minutes ofrun time has been reached and perform liq-liq extraction of floatingfatty material with nonpolar solvent. A rotary evaporator (orrotavap/rotovap) solvent from crude fatty phase to obtain anhydrousmaterial for characterization.

Result: 12 g fatty material, 1 wt % soap, 99 wt % FFA via titration.

-   -   Total energy usage: 1740 kWhr/metric ton FFA produced.

REFERENCES

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While the forgoing written description of the invention enables one ofordinary skill to make and use what is considered presently to be thebest mode thereof, those of ordinary skill will understand andappreciate the existence of variations, combinations, and equivalents ofthe specific embodiments, methods, and examples herein. The inventionshould therefore not be limited by the above described embodiments,methods and examples, but by all embodiments and methods within thescope and spirit of the invention. A number of embodiments of theinvention have been described. Nevertheless, it can be understood thatvarious modifications may be made without departing from the spirit andscope of the invention. Accordingly, other embodiments are within thescope of the following claims.

What is claimed is:
 1. A method for generating free fatty acids from amixed lipid feedstock using a thermal hydrolysis reaction, the methodcomprising: (a) providing an aqueous solution or mixture comprising amixed lipid feedstock, and wherein optionally the mixed lipid feedstockcomprises: a soapstock; a triglyceride comprising material; asaponifiable material, optionally a glyceride or a phospholipid; a talloil, optionally a “liquid rosin” tall oil, a soapstock; a gums product,optionally a chemically or enzymatically derived gums product; a crudebiodiesel; a fatty acid, optionally from a distillation bottom; a fatsplitter emulsion, optionally purged from fat splitter due toaccumulation when recycled; or, any combination thereof, and optionallythe mixed lipid feedstock comprises a soapstock, a wash-water comprisingsoaps or a combination thereof, optionally generated during the chemicalrefining of a crude natural oil, and optionally the mixed lipidfeedstock is derived from a biomass, a crude natural oil, or a plant oran animal source, optionally a tallow; and optionally the mixed lipidfeedstock is derived from enzymatic degumming of edible and inedibleoils; and (b) heating and pressurizing the aqueous solution or mixturecomprising the mixed lipid feedstock in a thermal hydrolysis reactionunder conditions comprising sufficient pressure and temperature togenerate a first reaction mixture comprising a free fatty acid and/or asoap, optionally a fatty acid salt, and/or a glyceride, optionally amonoacylglycerol (MAG), a diacylglycerol (DAG), or a triacylglycerol(TAG), wherein the thermal hydrolysis reaction is carried out at atemperature in the range of between about 20° C. to about 600° C., andat a pressure of between about 300 to about 2000 psig (about 20.7 bar toabout 137.9 bar), and for between about 1 second (sec) to about 3000minutes (min), or between about 1 min to about 300 min, or between about5 min to 200 min, and optionally the amount of water in the thermalhydrolysis reaction is between about 2:1 water-to-total dissolved solids(TDS) present in the mixed lipid feedstock to about 15:1 TDS, or about10:1 TDS; or between about 1:1 TDS present in the mixed lipid feedstockto about 100:1 TDS, and optionally a solvent is added to the thermalhydrolysis reaction in an amount of between about 0.01:1 water-to-totaldissolved solids (TDS) present in the mixed lipid feedstock to about100:1 TDS, or about 10:1 TDS.
 2. The method of claim 2, furthercomprising: (a) an acidification reaction that takes place after orduring or simultaneous with the thermal hydrolysis step, comprising: (1)providing an acid or an acid solution or a gas capable of forming anacid when mixed with water, optionally a carbon dioxide (CO₂) or a stackgas; and (2) combining or mixing the first reaction mixture with theacid or acid solution or the gas, optionally CO₂, or mixing the firstreaction mixture with the acid or acid solution or the gas, optionallyCO₂, to have an acidulation reaction and to generate a second reactionmixture, wherein the first reaction mixture is combined or mixed withthe acid or acid solution or the gas, optionally CO₂, for a sufficientamount of time to acidulate, optionally partially, or substantially allof, the soap in the first reaction mixture to generate free fatty acidsfrom the acidulated soaps, and optionally the pH of the acidulationreaction mixture is less than about pH 5, or is between about pH 1 to pH6, or is about pH 1, 2, 3, 4, 5 or 6, and optionally the amount of thegas is sufficient to increase the pressure of the reaction mixture,optionally in a reaction vessel, in which the acidulation reaction isbeing carried out to between about 0 and about 2000 psig. (b) the methodof (a), further comprising mixing the second reaction mixture with analcohol to form a third reaction mixture comprising fatty acid alkylesters, wherein optionally the mixing is done under conditionscomprising between about 240° C. to about 350° C., or 200° C. to 400°C., and a pressure of between about 1400 psi to about 3000 psi, andoptionally substantially all of the free fatty acids are esterified togenerate fatty acid alkyl esters, optionally, fatty acid methyl esters,and optionally the alcohol comprises methanol, ethanol or a mixturethereof; (c) the method of (a) or (b), further comprising separating,isolating, and/or purifying the free fatty acids and/or the fatty acidalkyl esters into separate fractions; or (d) a pre-treatmentacidification reaction step for treating the mixed lipid feedstockbefore the thermal hydrolysis reaction, wherein the pre-treatmentacidification reaction step comprises: (1) (i) providing an acid or anacid solution or a gas capable of forming an acid when mixed with water,optionally a carbon dioxide (CO₂) or a stack gas; and (ii) combining ormixing the mixed lipid feedstock with the acid or acid solution or thegas, optionally CO₂, or mixing the mixed lipid feedstock with the acidor acid solution or the gas, optionally CO₂, to have an acidulationreaction and to generate a pre-treated mixed lipid feedstock, whereinthe mixed lipid feedstock is combined or mixed with the acid or acidsolution or the gas, optionally CO₂, for a sufficient amount of time toacidulate, optionally partially, or substantially all of, the soap inthe mixed lipid feedstock; or (2) electrolysis, optionally using ahydrogen evolving cathode (HEC) electrolysis unit, of the mixed lipidfeedstock for a sufficient amount of time to acidulate, optionallypartially, or substantially all of, the soap in the mixed lipidfeedstock, and optionally the pH of the pre-treatment acidulationreaction mixture is less than about pH 5, or is between about pH 1 to pH6, or is about pH 1, 2, 3, 4, 5 or 6, and optionally the amount of thegas is sufficient to increase the pressure of the pre-treatment reactionmixture, optionally in a reaction vessel, in which the pre-treatmentacidulation reaction is being carried out to between about 0 and about2000 psig.
 3. The method of claim 1, wherein the natural oil or crudenatural oil comprises a vegetable oil, wherein optionally the vegetableoil comprises a soybean oil, a canola oil, a rapeseed oil, a corn oil, arice oil, a sunflower oil, a peanut oil, a sesame oil, a palm oil, analgae oil, a jatropha oil, a castor oil, a safflower oil, a grape seedoil or any combination thereof, and optionally the natural oil or crudenatural oil comprises castor oil, and optionally a free fatty acidgenerated is ricinoleic acid (12-hydroxy-9-cis-octadecenoic acid). 4.The method of claim 1, wherein the mixed lipid feedstock furthercomprises additional water, a phospholipid and/or an unsaponifiablematerial.
 5. The method of claim 2, wherein the acid or acid solutioncomprises carbonic acid, and optionally the carbonic acid is generatedby adding carbon dioxide (CO₂) to the first reaction mixture, therebycausing the carbon dioxide to react with water in the first reactionmixture to form carbonic acid, and optionally a source of the carbondioxide (CO₂) comprises a stack gas or a flue gas, or a gaseous CO₂emitted from an industrial process or an oven, a furnace, a boiler, asteam generator, a coal fired power plant, an ethanol plant, a brewery,or an industrial process wherein a gaseous waste stream comprising CO₂is emitted, and optionally the carbon dioxide is added to the firstreaction mixture, optionally as a liquid, a carbon dioxide gas, or as agaseous flow of carbon dioxide into the reaction vessel.
 6. The methodof claim 1, wherein the heating and pressurizing of the mixed lipidfeedstock is done in a single vessel, or sequential, different, reactionvessels; and optionally the pre-treatment and the thermal hydrolysis aredone in a single reaction vessel, and optionally the pre-treatment, thethermal hydrolysis and the post-thermal hydrolysis acidulation are donein the same reaction vessel.
 7. The method of claim 1, wherein: (a) thesoapstock is obtained from the alkaline neutralization of a crudenatural oil; (b) the gums product comprises phospholipids, andoptionally the gums product is generated during the degumming of anatural oil; or (c) the mixed lipid feedstock comprises, or furthercomprises, one or more compounds produced as a byproduct from the waterwashing of crude biodiesel, wherein optionally the compounds comprisesoapstock, monoglycerides, diglycerides, triglycerides and/or fatty acidalkyl esters or any combination thereof.
 8. The method of claim 1,wherein the method is a batch or a continuous process.
 9. The method ofclaim 1, wherein the heating and pressurizing the mixed lipid feedstocktakes place in conditions comprising: temperature in a range of betweenabout 100° C. to 500° C., or 200° C. to 400° C., or 240° C. to 300° C.,or at about 260° C.; and/or a pressure of between about 650 and 750psig, between about 750 and 850 psig, between about 850 and 1000 psig,between about 1000 and 1500 psig, or between about 1500 psig and 1800psig; and/or for between about 20 and 30 minutes, or between about 160and 180 minutes, or between about 300 minutes and 500 minutes.
 10. Themethod of claim 2, wherein the amount of gas is sufficient to increasethe pressure of the reaction mixture, optionally in a reaction vessel,in which the acidulation reaction is being carried out to between about10 and 1000 psig, about 20 to about 600 psig, about 30 to about 500psig, about 40 to about 400 psig, about 50 to about 300 psig, about 60to about 200 psig, about 60 to about 150 psig, about 70 to about 140psig, about 80 to about 120 psig, about 90 to about 110 psig, or about100 psig.
 11. The method of claim 2, wherein the acidulation reaction iscarried out at a temperature in the range of between about 5° C. toabout 400° C., e.g. about 10° C. to about 90° C., about 15° C. to about70° C., about 20° C. to about 60° C., or about 25° C. to about 40° C.12. The method of claim 2, wherein: (a) the acid or acid solutioncomprises an organic and/or an inorganic acid or a mineral acid, ahydrochloric acid, a sulfuric acid, a formic acid or sodium bisulfate,and optionally when a stack gas comprising N₂O, NO_(x), optionally NO₂,SO_(x), optionally SO₂, or H₂S is used the N₂O, NO_(x), SO_(x), or H₂Sreacts with water in the acidulation reaction mixture to form equivalentaqueous acid species; (b) after a reaction vessel has reached a desiredtemperature and pressure to carry out the acidulation step, theresulting reaction mixture is agitated, or otherwise mixed in order tomaximize the contacting of the soaps with the acid, optionally carbonicacid, and optionally the mixture can be agitated using a spinning blademixer, and optionally the mixture is agitated for between about 10minutes to about 200 minutes, e.g. between about 25 minutes to about 150minutes, or between about 20 minutes to about 60 minutes, or about 30minutes; (c) after the acidulation reaction, and optionally following anagitation step, the contents of the acidulation reaction, optionally ina reaction vessel, are allowed to settle or partition allowing for theformation or separation of a lipid layer, a lipid phase or a lipidcomponent, and an aqueous layer, an aqueous phase or an aqueouscomponent, wherein the lipid layer or lipid phase floats on the top ofthe aqueous layer, and optionally the lipid layer or lipid phasecomprises free fatty acids and any non-acidulated soaps, and the aqueouslayer comprises water, glycerol, phosphate salts, sodium bicarbonate,sodium carbonate or other equivalent salts, unsaponifiable material,optionally waxes and sterols, and dissolved carbonic acid; (d) themethod of (c), wherein before or after the reaction products of theacidulation reaction, optionally in a reaction vessel, are allowed tosettle or partition, the reaction products of the acidulation step aretransferred to a separation vessel, optionally a decanter, a settler oran equivalent, or a centrifuge where the lipid layer or lipid phase orcomponent separates or partitions out from an aqueous phase orcomponent; or the acidulation product mixture is not transferred to aseparate vessel in order to separate lipids in the lipid layer or lipidphase from reaction products in an aqueous phase or component, and afterthe lipid layer or lipid phase or component separates or partitions outfrom the aqueous phase or component the aqueous layer is drained fromthe bottom of the reaction vessel and the lipid layer or the lipid phaseor component is recovered as the reaction product; (e) furthercomprising multiple acidulation reactions, optionally between about 1and 20 additional acidulation reactions, or about 1, 2, 3, 4, 5, 6, 7 or8 or more additional acidulation reactions; or (f) after the acidulationreaction the reaction vessel is depressurized, allowing for dissolvedcarbonic acid or other gaseous acid to separate out of the solution asgaseous CO₂, or equivalents, and optionally captured CO₂ is recycled foruse in the further acidulation reactions.
 13. The method of claim 1,wherein the solvent added to the thermal hydrolysis reaction is a polar,optionally a methanol, or a non-polar, optionally a hexane, solvent. 14.The method of claim 2, wherein the thermal hydrolysis reaction and theacidulation reaction take place sequentially; or, the thermal hydrolysisreaction and the acidulation reaction can take place simultaneously as a“one pot” reaction in one reaction vessel.
 15. The method of claim 12,wherein the lipid layer or lipid phase or component, optionallycomprising unreacted soaps, is transferred to an electrolysis unit,optionally a hydrogen evolving cathode (HEC) electrolysis unit, whereinthe lipid layer or lipid phase or component is reacted with an anolytesuch that the unreacted soaps generate free fatty acids, and optionallythe electrolysis step converts substantially all, or about 90%, 95%, 98%or more of the unreacted soaps to free fatty acids, wherein optionallythe anode comprises a mixed metal oxide (MMO) layer coated onto a stablemetal substrate, optionally a titanium, and optionally the anolytecomprises a sodium or potassium sulfate, a sodium or potassium nitrate,or a sodium or potassium chloride.
 16. The method of claim 12, whereinthe lipid layer or lipid phase or component is transferred to anelectrolysis unit, optionally a hydrogen evolving cathode (HEC)electrolysis unit, comprising a vessel or suitable container comprisingan anode, optionally an anode vessel, and a vessel or other suitablecontainer comprising a cathode, optionally an cathode vessel, separatedby a selective filtration membrane, optionally a polytetrafluoroethylene(PTFE) membrane, wherein optionally the anode comprises a mixed metaloxide (MMO) layer coated onto a stable metal substrate, optionally atitanium, and optionally the cathode comprises a titanium or a Monelalloy, or any substrate that is stable in a reducing environment. 17.The method of claim 12, wherein the aqueous phase or component, ormultiple aqueous phases if collected from multiple acidulationreactions, is treated to remove water, wherein optionally the treatmentof the aqueous phase or component to remove water is by a drying method,optionally evaporation via falling film, forced recirculation flashingor equivalent, thereby generating a product comprising sodiumbicarbonate, and optionally the product is dried further to generate asodium bicarbonate product that is substantially free of any water,optionally less than about 20% water or less than about 10% water, andoptionally the drying is done using a fluidized bed dryer, alyophilizer, a spray dryer, or a rotary drum dryer.
 18. The method ofclaim 12, wherein the aqueous phase or component, or multiple aqueousphases if collected from multiple acidulation reactions, is treatedusing a filtration, optionally a membrane filtration system, a nano- ormicrofiltration system or a size-exclusion filtration system, andoptionally the filtration is operationally in-line operatingcontinuously with the acidulation step such that aqueous phase generatedin the acidulation reaction, or each acidulation reaction if more thanone acidulation reaction, is treated immediately after or during thepoint at which the aqueous phase is separated from the lipid phase, andoptionally the aqueous phase is collected and treated in a single batch,and optionally soaps and/or other saponifiable material rejected by thefiltration, optionally soaps and/or other saponifiable material that donot pass through a membrane of a filter system, are returned to thelipid layer or lipid phase or component for subsequent acidulationreactions, thereby increasing the overall fatty acid yield.
 19. Themethod of claim 12, wherein the aqueous phase or component, or multipleaqueous phases if collected from multiple acidulation reactions, istreated with calcium hydroxide, optionally a slaked lime, to form acalcium precipitate, optionally a calcium phosphate (Ca_(x)(PO₄)_(x))precipitate, and optionally the lime-treated aqueous phase or component,or multiple aqueous phases if collected from multiple acidulationreactions, is subjected to an oxidation step, optionally a Fentonoxidation wherein hydrogen peroxide and Fe²⁺ ions are used to catalyzeOH radical formation.
 20. The method of claim 12, wherein the aqueousphase or component, or multiple aqueous phases if collected frommultiple acidulation reactions, is subjected to electrolysis to recovermonovalent ions as a base for a value added product, wherein electricalcurrent is passed through a cathode, the water is reduced, therebygenerating hydroxide ions; and as monovalent ions, optionally sodium orpotassium, are pushed across a membrane separating an anode vessel froma cathode vessel into the cathode vessel, they react with the generatedhydroxide ions to generate a corresponding hydroxide base, optionally asodium hydroxide or a potassium hydroxide, and optionally the hydroxidebase separated out, recovered and/or isolated.